CS205679B1 - Method of cyclotrimerization of the butadien to the 1,5,9-cyclododekatrien under presence of the catalyser on the basis of titanium - Google Patents
Method of cyclotrimerization of the butadien to the 1,5,9-cyclododekatrien under presence of the catalyser on the basis of titanium Download PDFInfo
- Publication number
- CS205679B1 CS205679B1 CS47479A CS47479A CS205679B1 CS 205679 B1 CS205679 B1 CS 205679B1 CS 47479 A CS47479 A CS 47479A CS 47479 A CS47479 A CS 47479A CS 205679 B1 CS205679 B1 CS 205679B1
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- Czechoslovakia
- Prior art keywords
- tetra
- cyclotrimerization
- titanate
- cyclododecatriene
- titanium
- Prior art date
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 19
- 238000006006 cyclotrimerization reaction Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 7
- 229910052719 titanium Inorganic materials 0.000 title claims description 5
- 239000010936 titanium Substances 0.000 title claims description 5
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 claims description 12
- -1 2-isopropoxyphenyl Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- SXIFNAOBIAIYJO-SXVCMZJPSA-N (1E,3E,7E)-cyclododeca-1,3,7-triene Chemical compound C/1=C\CCCC\C=C\C=C\CC\1 SXIFNAOBIAIYJO-SXVCMZJPSA-N 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález se týká způsobu cyklotrimerizace butadienu na 1,- 5, 9-cyklododekatrien za přítomnosti katalyzátoru ná bázi tetra(alkoxyfenyl)titanátů.The present invention relates to a process for cyclotrimerization of butadiene to 1, 5, 9-cyclododecatriene in the presence of a catalyst based on tetra (alkoxyphenyl) titanates.
Dosud známé způsoby cyklotrimerizace butadienu za použití katalytických systémů na bázi alkyltitanátů poskytují 1, 5, 9-cyklododekatrien s výtěžkem pouze 80 až 90%, viz jap. pat 7 3Ό5 575 (1973) a Takahashi H, Yamaguchi M.: I. Org. Chem. 28, 1409 (1963).Hitherto known methods of cyclotrimerization of butadiene using catalytic systems based on alkyl titanates give 1,5,9-cyclododecatriene in yields of only 80 to 90%, see jap. Pat 7 3-557 (1973) and Takahashi H, Yamaguchi M .: I. Org. Chem. 28, 1409 (1963).
je-ii v katalytickém systému použito . tetra(aryl)titanátu, selektivita se ještě zvýší. Jeden z nejefektivnějších katalytických systémů je popsán v jap. pát. 7 307 620 (1973), kde vzniká až 92 % 1, 5, 9-cyklododékatrienu. Uvedený systém však obsahuje 70 molů velmi drahé organohlinitě složky na 1 mol titanu, což velmi zvýrazňuje jeho cenovou nevýhodnost.when used in a catalytic system. tetra (aryl) titanate, selectivity is further increased. One of the most efficient catalytic systems is described in jap. Fri. 7,307,620 (1973), where up to 92% of 1,5,9-cyclododecatriene is formed. However, the system contains 70 moles of the very expensive organoaluminum component per 1 mol of titanium, which greatly emphasizes its cost disadvantage.
Uvedené nedostatky odstraňuje způsob cyklotrimerizace butadienu na 1, 5, 9-cyklododekatrien za přítomnosti katalyzátoru na bázi titanu, jehož podstatou je, že se k reakci použijí katalyzátory na bázi tetra (2-alkoxyf enyl Jtitanátů, výhodně tetra(2-metoxyfenyl)titanát, tetra{2-etoxynef enylj titanát, tetra (2-izopropoxyf enyl) titanát nebo tetra(2-fenoxyfenyl)titanát.These drawbacks are eliminated by the process of cyclotrimerization of butadiene to 1,5,9-cyclododecatriene in the presence of a titanium-based catalyst, which consists in using tetra (2-alkoxyphenyl) titanate catalysts, preferably tetra (2-methoxyphenyl) titanate, tetra (2-ethoxyphenyl) titanate, tetra (2-isopropoxyphenyl) titanate or tetra (2-phenoxyphenyl) titanate.
Tetra (alkoxyfenyl) titanát obecného vzorce ; 2 se redukuje alkylaluminiumchloridem obecného vzorce Ri AlCI3.n, kde R1 je metyl, etyl, propyl, butyl, izobutyl, fenyl a n je 1,3 až 2,2, v prostředí aromatických nebo chlorovaných aromatických uhlovodíků za přítomnosti butadienu nebo v inertní atmosféře. Takto vzniklý katalyzátor obsahuje minimálně vysokomolekulárních polymerů.Tetra (alkoxyphenyl) titanate of the general formula; 2 is reduced with an alkyl aluminum chloride of the formula R 1 AlCl 3 . n wherein R 1 is methyl, ethyl, propyl, butyl, isobutyl, phenyl and n is 1.3 to 2.2, in an aromatic or chlorinated aromatic hydrocarbon environment in the presence of butadiene or in an inert atmosphere. The catalyst thus formed contains at least high molecular weight polymers.
Způsobem podle vynálezu vzniká nejméně 93,5 proč. 1, 5, 9-cyklododekatrienu, přičemž nutný obsah organohlinité složky nepřevyšuje 20 mol na 1 mol titanu.The process of the invention produces at least 93.5 why. 1,5,9-cyclododecatriene, wherein the necessary organoaluminum component content does not exceed 20 mol per 1 mol of titanium.
Nízká spotřeba hlinité komponenty, vysoký výtěžek produktu a snadná příprava Ti-složky umožňují získat 1, 5, 9-cyklododekatrien cenově podstatně výhodněji než u dosud známých způsobů.The low consumption of the aluminum component, the high yield of the product and the easy preparation of the Ti-component make it possible to obtain 1,5,9-cyclododecatriene at a significantly lower cost than in the prior art processes.
Vynález je blíže objasněn v následujících příkladech provedení.The invention is illustrated by the following examples.
Příklad 1 .Example 1.
K 1 mmolu (tetra (2-etoxyfenyl)titanátu ve 170 ml toluenu bylo v atmosféře dusíku při 40 °C přidáno 20 mmol- Et3Al2Cl3. Teplota byla zvýšena.na 50 °C a do reaktoru zaveden butadien. Butadien byl po celou dobu přiváděn v mírném přebytku, reakce byla po 5 hodinách ukončena rozložením katalyzátoru. Bylo získáno 800 g olígomerů, výtěžek II, 5, 9-cyklododekatrienu činil 94 % hmot., obsah polymerů byl nižší než 1,0 proč. hmot.To 1 mmol (tetra (2-ethoxyphenyl) titanate in 170 ml of toluene) was added 20 mmol of Et 3 Al 2 Cl 3 under nitrogen atmosphere at 40 ° C. The temperature was raised to 50 ° C and butadiene was introduced into the reactor. The reaction was terminated after 5 hours by decomposition of the catalyst to give 800 g of oligomers, yield of II, 5, 9-cyclododecatriene was 94% by weight, the polymer content was less than 1.0% by weight.
0 5 S 7 90 5 E 7 9
205673205673
Příklad 2Example 2
Cyklotrimerizací butadienu podle příkladu 1 vzniklo za 15 hodin 1700 g oligomerů butadienu, výtěžek 1, 5, 9-cyklododekatrienu činil 94 % hmot.The cyclotrimerization of butadiene according to Example 1 yielded 1700 g of butadiene oligomers in 15 hours. The yield of 1,5,9-cyclododecatriene was 94% by weight.
Příklad 3Example 3
Cyklotrimerizací butadienu podle příkladu 1 při 47 °C byla získána reakční směs o složení 1,3 % cyklodimerů, 94,4% hmot. 1, 5, 9-cyklododekatrienu, 3,1 % hmot. oligomerů a 1,2 % hmot. vysokomolekulárních polymerů.Cyclotrimerization of butadiene according to Example 1 at 47 ° C yielded a reaction mixture of 1.3% cyclodimers, 94.4% by weight. % 1,5,9-cyclododecatriene, 3.1 wt. % of oligomers and 1.2 wt. high molecular weight polymers.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS47479A CS205679B1 (en) | 1979-01-22 | 1979-01-22 | Method of cyclotrimerization of the butadien to the 1,5,9-cyclododekatrien under presence of the catalyser on the basis of titanium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS47479A CS205679B1 (en) | 1979-01-22 | 1979-01-22 | Method of cyclotrimerization of the butadien to the 1,5,9-cyclododekatrien under presence of the catalyser on the basis of titanium |
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| Publication Number | Publication Date |
|---|---|
| CS205679B1 true CS205679B1 (en) | 1983-07-29 |
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| CS47479A CS205679B1 (en) | 1979-01-22 | 1979-01-22 | Method of cyclotrimerization of the butadien to the 1,5,9-cyclododekatrien under presence of the catalyser on the basis of titanium |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1323723A4 (en) * | 2000-10-05 | 2004-08-04 | Idemitsu Petrochemical Co | TRANSITION METAL COMPOUNDS, POLYMERIZATION CATALYSTS FOR OLEFINS, OLEFIN POLYMERS AND METHOD FOR THEIR PRODUCTION |
-
1979
- 1979-01-22 CS CS47479A patent/CS205679B1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1323723A4 (en) * | 2000-10-05 | 2004-08-04 | Idemitsu Petrochemical Co | TRANSITION METAL COMPOUNDS, POLYMERIZATION CATALYSTS FOR OLEFINS, OLEFIN POLYMERS AND METHOD FOR THEIR PRODUCTION |
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